Magnetic recording media generally include a binder dispersion layer comprising a binder and a pigment overlying a substrate, wherein the pigment is dispersed within the binder. Typically, the pigment is a magnetizable pigment comprising small, magnetizable particles. In some instances, the medium may be in the form of a composite having both back-coat and front-coat binder dispersion layers, although the pigment in the back-coat may or may not be a magnetizable pigment.
It has become desirable to have as high a loading of magnetizable pigment in the magnetic recording media as is reasonably possible. It is often preferred to have a binder dispersion comprising from about 70% to 85% by weight magnetizable pigment relative to the binder with as many magnetizable particles per unit area or unit volume as possible. It is also preferred to have a binder dispersion in which the magnetizable pigment comprises a plurality of small particles having a relatively high specific surface area. Higher pigment loading has the potential to provide high density magnetic recording media capable of storing more information.
Problems, however, remain in the art concerning magnetic recording media having a relatively high loading of magnetizable pigment. To begin with, magnetizable pigments tend to agglomerate, and they are difficult to properly and fully disperse within the binder. Wetting agents, or dispersants, are often employed to facilitate such dispersion. For higher pigment loading, i.e., the use of greater amounts by weight and number of magnetizable particles, greater amounts of such dispersants are required, which is not always desirable. There are a number of reasons for using as little dispersant as possible. Costs, for example, can be reduced by using less dispersant. Additionally, binder dispersions can be more readily and reproducibly prepared when less dispersant is used. Further, excess dispersant may have a tendency to bloom from a cured binder dispersion over time, leading to contamination of a recording head or the like, or causing a change in the physical or chemical characteristics of the media.
Another problem in the art is that the viscosity of a binder dispersion generally increases with higher loading of magnetizable pigment. If the dispersion is too viscous, it can be difficult to apply to the substrate, and good magnetic orientation of the pigment, i.e., a squareness ratio of 0.75 or more, can be hard to obtain. The squareness ratio (Br/Bm), which is the ratio of the remnant saturation induction, or residual magnetization (Br), to the saturation induction, or saturation magnetization (Bm), refers to the effectiveness of the orientation of the magnetic particles. For randomly-oriented particles, the squareness ratio is 0.5 and for ideally and perfectly oriented particles, the ratio is equal to 1.0. Values for the squareness ratio, of media exhibiting good performance, normally fall around 0.75 to 0.85. In general, an increase in the squareness ratio is reflected by an improvement in orientation characteristics and electromagnetic properties.
To help alleviate these problems with high pigment loading, binder compositions having internal dispersants have been developed. Such compositions comprise polymers with functional moieties pendant from the polymer backbone that help disperse the magnetizable pigment. As a result of using these compositions, less dispersant is needed for dispersion of magnetizable pigment in the binder.
Copending U.S. application Ser. No. 07/429,720, filed Oct. 31, 1989, now U.S. Pat. No. 5,071,578 which is a continuation-in-part of U.S. application Ser. No. 07/295,046, filed Jan. 6, 1989 (assigned to the assignee of the present case) discloses a curable polymer having internal dispersants which comprises a sulfonated, hydroxy-functional polyurethane (SHPU) resin. The SHPU resin can be used as part of a binder layer in magnetic recording media. The application discloses the excellent dispersion of magnetizable pigment within the SHPU resin and the ease of application of the dispersion onto a suitable substrate.
There are, however, certain types of media constructions where high glass transition temperature (Tg) and abrasion resistance in the uncured state, and high final coating modulus are both desirable and necessary, for example, where stiffer tapes are needed for better handling in the recording and playback machine, or where manufacturing methods dictate the necessity of having high initial strength coatings that are resistant to damage during manufacture or processing.
In order to increase the durability, running properties, and reliability of magnetic recording media, attempts have been made to add a hard material to the pigment-containing binder.
U.S. application Ser. No. 07/315,304, filed Mar. 1, 1989 (assigned to the assignee of the present case) discloses a curable magnetic binder composition which comprises a curable sulfonated, hydroxy functional polyurethane which is combined with another polymer, usually called a "hard resin", to attain the desired high T.sub.g for optimum binder performance in certain applications. The "hard resin" disclosed in Ser. No. 07/315,304 is a cross-linkable hydroxy functional vinyl chloride having incorporated therein SO.sub.3 M groups wherein M represents H.sup.+ or a metal cation. Although polymer blends of the type disclosed in Ser. No. 07/315,304 are very useful, the dispersing character of the binder system can sometimes diminish. In addition, only a few types of hard resins have been found to be functional because of a general lack of polymer/polymer compatibility. For example, hard resins based upon acrylic monomers have not been found to be usefully compatible with the preferred types of polyurethane binder resins.
In order to optimize binder performance single polymer systems have been developed in which a "hard resin" is grafted onto a polyurethane having pendant hydroxy and sulfonate groups rather than blended therewith.
Copending, concurrently filed U.S. patent application Ser. No. 07/543,343, Carlson et al., (assigned to the assignee of the present case) discloses vinyl/SHPU copolymers made via the utilization of macromonomer diols and sulfonate diols. The method generates quality material; however, it is limited as to the selection of monomers that can be used (i.e., non-hydroxy functional monomers).
Copending, concurrently filed U.S. patent application Ser. No. 07/543,230, Kumar et al., (assigned to the assignee of the present case) describes sulfonated, hydroxy and thiol functional polyurethanes and graft copolymers made therewith via free radical polymerization of vinyl monomer in the presence of the sulfonated, hydroxy and thiol functional polyurethane. Although the method has a number of distinct advantages it does not provide for a high degree of tailorability of the copolymers prepared therewith.
A need thus exists for a single polymer magnetic binder system which does not need to be blended with a hard resin, which can be "tailor" made from a wide variety of monomers so that a wide spectrum of physical properties can be introduced, which possesses a high T.sub.g, which possesses good mechanical properties, which disperses pigment well, and which is capable of being cross-linked by isocyanate curatives.
We have found such a copolymer which is prepared via photoiniferter technology. Photoiniferter technology is a recently developed technology which allows for the polymerization of block copolymers from various monomers. The control of the polymerization provided by the photoiniferter technology permits "tailoring" of the block copolymers formed thereby so that a polymer having a wide spectrum of physical properties can be prepared. Such high precision tailoring is not possible with previously known polymerization methods such as thermal polymerization.
The term "iniferter", or "photoiniferter" as it is also known, refers to a chemical compound that has a combined function of being a free radical initiator, transfer agent, and terminator, the term "iniferter" being a word formed by the underlined portions of the terms identifying these functions. The photo portion of the term indicates that the polymerization is photolytically induced. This term and its use in the production of block copolymers is well known, particularly because of the work of Takayuki Otsu of the Department of Applied Chemistry, Osaka City University, Osaka, Japan. This work is discussed, for example, in an article by Otsu et al entitled "Living Radical Polymerizations in Homogeneous Solution by Using Organic Sulfides as Photoiniferters", Polymer Bulletin, 7, 45-50 (1982), an article by Otsu et al entitled "Living Mono-and Biradical Polymerizations in Homogeneous System Synthesis of AB and ABA Type Block Copolymers", Polymer Bulletin, 11, 135-142 (1984), and in European Patent Application No. 88303058.7, Publication No. 0 286 376, Publication Date Oct. 12, 1988.
Copending U.S. application Ser. No. 07/356,650, filed May 19, 1989, which is a Continuation-In-Part of U.S. application Ser. No. 07/212,594, Ali, et al., filed Jun. 28, 1988 (assigned to the assignee of the present case) discloses the use of iniferter technology in the preparation of acrylic block copolymers having the requisite physical properties making them suitable for use in pressure-sensitive adhesive compositions.
Copending U.S. application Ser. No. 07/212,593, Andrus Jr. et al., (also assigned to the assignee of the present case) discloses the use of iniferter technology in the preparation of acrylic block copolymers which can be tailored to provide optical clarity and resistance to oxidative and photochemical degradation.
Copending U.S. application Ser. No. 07/393,550, Kumar, et al. now U.S. Pat. No. 5,057,619 (assigned to the assignee of the present case) provides novel siloxane macroiniferter compounds which can be used in making tailor-made vinyl-siloxane block copolymers.
To our knowledge there has been no use of iniferter technology in the preparation of vinyl/SHPU or vinyl/hydroxy-functional polyurethane (vinyl/HPU) graft or block copolymers. Nor has there been any use of such polymers in magnetic recording media.